Hydrochloric Acid → (e)-2-[1-(2,5-Dimethyl-3-furyl)ethylidene]-3-isopropylidenesuccinic anhydride

HRID 1708601

反応式

HRID 1708601 の反応式
[H-].[Na+].[C:3]([C:6]1[CH:10]=[C:9]([CH3:11])[O:8][C:7]=1[CH3:12])(=O)[CH3:4].[C:13]1(=[O:27])[O:26][C:19](C)([CH:20]([CH2:23]C)[CH2:21][CH3:22])[O:18]C(=O)CC1.Cl.[C:29](Cl)(=O)C>C(Cl)(Cl)Cl.C1C=CC=CC=1>[CH3:12][C:7]1[O:8][C:9]([CH3:11])=[CH:10][C:6]=1/[C:3](=[C:23]1/[C:13]([O:26][C:19](=[O:18])[C:20]/1=[C:21]([CH3:22])[CH3:29])=[O:27])/[CH3:4]

参加物

8

反応物 5

HCID 313Hydrochloric AcidHCID 6367Acetyl chlorideHCID 24758Sodium hydrideHCID 615273-Acetyl-2,5-dimethylfuranHCID 54162692Diethylisopropylidene succinate

生成物 1

HCID 13735569(e)-2-[1-(2,5-Dimethyl-3-furyl)ethylidene]-3-isopropylidenesuccinic anhydride収率 15%

試薬・触媒・溶媒 2

HCID 241Benzene溶媒HCID 6212Chloroform溶媒

実験手順

To a suspension of 700 ml of benzene with 52.8 g of sodium hydride, 118 g of a mixed solution 76 g of 3-acetyl-2,5-dimethylfuran (mfd. by Sldrich Chemical Co., Inc.) and 118 g of the diethylisopropylidene succinate obtained in Reference Example 1 (4) was added dropwise in 2 hours with stirring. After reacting for further 7 hours with stirring, the reaction solution was poured into 2 kg of ice. The water layer was separated, made acidic with 690 ml of 5M HCl, and extracted with 1.5 liters of ethyl acetate. The resulting organic layer was concentrated. To the residue, 1.85 liters of 5 w/v% ethanolic potassium hydroxide was added and reaction was carried out for 15 hours under relux. After the reaction, the reaction solution was made acidic with HCl. A precipitate produced was dissolved in chloroform. The solvent was removed from the resulting chloroform solution by distillation. To the residue, acetyl chloride was added and ring closing reaction was carried out. After the reaction, excess acetyl chloride was removed by distillation. The residue was purified by column chromatography (filler: Wakogel C-300, eluent: a mixed solvent of n-hexane and ethyl acetate) to give pale yellow crystals of 2-[(E)-1-(2,5-dimethyl-3-furyl) ethylidene]-3-isopropylidene succinic anhydride of the formula: ##STR26## wherein Me is a methyl group, in yield of 15%.

後処理

  1. additionwas added dropwise in 2 hours
  2. stirringwith stirring
  3. customThe water layer was separated
  4. extractionextracted with 1.5 liters of ethyl acetate
  5. concentrationThe resulting organic layer was concentrated
  6. additionTo the residue, 1.85 liters of 5 w/v% ethanolic potassium hydroxide was added
  7. customreaction
  8. waitwas carried out for 15 hours under relux
  9. customAfter the reaction
  10. customA precipitate produced
  11. customThe solvent was removed from the resulting chloroform solution by distillation
  12. additionTo the residue, acetyl chloride was added
  13. customring closing reaction
  14. customwas removed by distillation
  15. customThe residue was purified by column chromatography (filler

出典と根拠

ORDレコード
ord-60f8d18dc35546979533157f6a39eb1f
出典データセット
uspto-grants-1994_10
特許番号
US05359085

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